Cyanalkyl ether plasticizers and synthetic resin compositions plasticized therewith



Patented May 15, 1951 CYAN'ALKYL ETHER PLASTICIZERS AND SYNTHETIC RESIN COMPOSITIONS PLASTICIZED THEREWITH Donald Faulkner, Epsom, England, assignor to The Distillers Company Limited, Edinburgh, Scotland, at British company No Drawing. Application December 2, 1948, Se-

rial No. 63,192. In Great Britain December 17,

11 Claims. (Cl. 26032.4)

,The present invention relates to the plasticisa- I XCH-OR where X is phenyl, halogen-substituted or alkyl substituted phenyl and R. is, inter alia, a saturated carbon chain containing at least one hydroxyl group, and it has already been proposed,

' in United States Patent No. 2,280,790, to use as plasticisers betacyanalkyl ethers of monohydric alcohols having an aliphatic chain or cycle interrupted by one or more oxygen or sulphur atoms, for example, betacyanethyl betaphenoxyethyl ether and the betacyanethyl ether of glycol monobenzyl ether.

We have now discovered that compounds having the general formula where X1 is phenyl, monoor dichlor-substituted phenyl or monoor dimethyl substituted phenyl, R1 is an alkylene radical of 2, 3 or 4 carbon atoms, to each of which carbon atoms is attached at least 1 hydrogen atom, and n is 1 or 0, are plasticisers for polymeric compounds comprising vinylidene chloride units, showing improved compatibility as compared with their hydroxy analogues containing a hydroxyl group in place of the cyano group, and considerably improved stability (resistance to autoxidation) as compared with the corresponding benzyl alcohol derivatives. When n is in' the above formula, the formula then becomes It will be appreciated that an alkylene radical having at least two carbon atoms is derived by removal of an atom of hydrog n from each of two different carbon atoms of a saturated aliphatic hydrocarbon, and is to be distinguished from the isomeric alkylidene radical, which is derived by removal of two atoms of hydrogen from a single carbon atom of the hydrocarbon.

The cyanalkylether plasticisers are believedto be new compounds. The cyanethyl ethers may be prepared by the condensation of acrylonitrile with the corresponding alcohols, namely phenyl methyl carbinol, its glycol ether or their nuclear substituted derivatives specified above; the 2- cyanpropyl and the cyanisopropyl ethers may be prepared similarly from methacrylonitrile and allyl cyanide or crotononitrile respectively, While the primary cyanpropyl and cyanbutyl ethers may be prepared by condensing styrene with 3-chlorpropanol or 4-chlorbutanol and subsequently reacting the chlorether thus produced with, say, sodium cyanide.

Suitable proportions of the cyanalkyl ethers in the plasticised compositions of the present invention are in the range 5-20% by weight of the resin, and it has been found that, in this range the plasticiser also exerts a stabilising effect in retarding the breakdown of the constituent vinylidene chloride units under the influence of heat and light. I

The following six examples illustrate the preparation of representative members of the novel class of plasticisers:

Example 1 0.2 g. of sodium was dissolved in a solution of 30 g. of phenylmethyl carbinol in 50 ml. of henzene. This solution was warmed to 40 C., and 13 g. of acrylonitrile was added slowly, the tem perature being kept at 40-45 C. by cooling. When the addition was complete, the temperature was maintained at 40-45 C. for 1 hours, after which the solution was washed with dilute hydrochloric acid, then with water and dried. Removal of the benzene by distillation and fractionation of the residue gave 34 g. of alphamethylbenzyl betacyanethyl ether, b. pt. (1 mm. Hg) 72-'74 C., n 1.5045.

Example 2 25 g. of beta(alphamethylbenzyloxy) ethanol (prepared from styrene and ethylene glycol) were reacted with 6 g. acrylonitrile by the method described in Example 1, using the same times and temperature ranges. 24 g. of alphamethylbenzyl betacyanethoxyethyl ether were obtained, b. pt. (1 mm. Hg) 102-104" C., n 1.5000.

Example 3 for 4 /2 hours, at 95-100 C. .tor.8 hoursandflnally at 1l0-115 C. for 3 hours. 1-.-Aften-ewashing-with=- water, a little chloroform being added lto'iaid separation, the mixture was fractionall distilled under 15 mm. Hg pressure to"givei25. g i'of'styrene, a fraction b. pt. 64-70 C: containing alphachlorethyl benzene and a residue. residue at 1-2 mm. Hg 'pressure' .gavei 2acg liof material b. pt. 70-'75 C., refraetionatioziof which i gave 24 g. of alphamethylbenzyl 4-chlorbutyl ether b. pt. (1 mm. Hg) 64-67 C.,;in'D 9,.l .5G20.

A solution of 12 g nof sodium cyanide in 18 .ml.. of water was added. to asolution, 01.30 g..of .ithisfihlofether ,inTlOOjinLjof ethanol, a'ndjthe '..'mixture was refluX'edifo'r 7. hours. I Aftercoolin 'Iftheimixture wasf'filtered,t0 .remove sodium chloride, and as. much ethanol as possible was distilled. from thefiifiltrate. under, I50- ,mmL Hg.

1 'pressure. .The residuemas .washed with water fphenone. andsodiumi'ethylate. ina1'cohol,;as,de scribed Gaz'. "Chimi' Ital. 45,!II )1 2.72). .and -18 ,g. of. acrylonitrilev were condensed inigthe pres-:-

""ence'of 0135. g. .of sodium andj60 m1. 'o'f,.benzene 'by." thetprocess desCribedirilExarriple 1. .After "'wash ing and. fractionating" .there were obtained :43 g. (83%t'yield) of .,alphamethyl ..parachlor- "tben'zyl betacyan'ethyl ether, b. .ptl'. (6-32 -mmQI-Ig) "I 140-150 C., .15 1.5230.

Example 5 .7175" f alphaxylyl ethanol,(i. .e.amethyl .2 4 dimethylphenylc'afbinol, describedin. rZBerichte 35, 2248, and in Berichte 47, 2461) and 26.5 g. of acrylonitrile were.-condensed in the presence i 0.25 g. of sodium in the absence 015.. any *"di'luentfbutjotherwise as described inExample 1. 1 "After viashingand fractionating there .weref.obtained 73 g. 172%.- yield) "of.,alphamethyl 2:4..di-

methyl "benzyl :betacyanethyl ether, b. ,ptLJll-Z mm. Hg) "150 151i.C:,, 71, 125170.

.2 Example 6 0.2 gzof sodium were-"dissolved in aysolution ef-230 gsfof phenyl methylgcarbinol in '50 .ml..iof -*dry benzene, followedby 1'7 g. of allyl: cyanide. *The "mixture'was heated'at 65-70? C. while stirfiring for 22: hoursi -then "washed withfdilute. hy-- drochloric acid and with water, and-freed from benzene by distillationl ;Fractionation of the residual liquidnnder.reducedipressure gave-14.4 g. of .unre'acted phenyl. niethylca'rbi-nol, .followed Pf y 9.8 g.:' of. crudereaction product, b...pt. .1001

Distillation of the" 4 107 C. under 1 mm. Hg pressure. Refractionation of this material afforded 17.0 g. of pure alphamethylbenzyl betacyanisopropyl ether, b. pt. 103-105 C. under 1 mm. Hg pressure, n 1.4964.

Other alcohols which may be subjected to cyanalkylation with acrylonitrile, alphamethacrylonitrile, allyl cyanide or crotononitrile to give members of the novel class of plasticisers of the present invention may be prepared by Q... hydration of lithe now "commercially; available corresponding methyl-g d-lm'ethyl-fc'hioror dichlor styrenes, or they may be prepared by -i known' procedures, for example, by reduction of .the corresponding ketones or by Grignard s'yn- Thus, methyl- 3:4rdimethylphenyl carbinol has been prepared by reduction of 3:4 dimethylaceto- '-phenone-j(J,. prfiGhem. (2) 41, 410), methyl 2:5 "dimethylphenyl' carbinol has been prepared from "2:5"'dimethylacetophenone (Berichte 36, 1639), .zrmet-hyl :3::5:':'.d-imetliylpheny1 carbinol has been .rpreparedvfrom iacetaldehyde and 3:5 dimethylphenyl magnesium bromide (Berichte 58, 4'7), .methyl 2 :4 dichlorphenyl carbinol has been pre- 25 pared from 2:4 dichlorphenyl magnesium iodide and acetaldehyde (JCS,. 1927, p., .1164)... and :methyli 2-chlorphenyl 'carbinol has ,beenmprepared from" methyl" magnesium bromide and 2- *i'chlorbenzaldehyde' (Berichte58, 9.). w The following"examples illustrate the use jof the novel cyanalkyl ethers'in vinylidene; chloride resin compositions.

liEmample 7 1 part by weighti-ofalphamethylbenzyl ":beta- ----cya-nethyl ether-was intimately mixed :withflO parts by weight of a copolymer containing 89% w./w. of vinylidenechloride, 10% of vinyl chloride, and 1% of acrylonitrile by stirring with 40 acetone and then removing the acetone by evaporation. "The composition so *-obtained--consisted 'of' a fine-' whitepowder; which was-then" compressed into pellets. These were fed intOthe barrelof asmall-extrusionmachinercenstructed g of nickehand actuated by a piston. 'Fhe ma- 'c'hine'wa's fitted with anozzle e y in diameter, and the-barrel and nozzle were-heated to'"-1?0 .i C. "The composition was extruded through the 1. nozzle-toform a clear pale-yellow monofilameint 0f: 'high strengthfi The degree of -fiow- 'was' very satisfactory, and no signs of decompositionwere observed. V

The above procedure was repeated with a= copolymerncontaining .90 .w-./ W; :?of;. 'avinylidene chloride and 10% of vinyl chloride. An almost colourless monofilament was obtained.-and the fiow properties "of the composition "were very satisfactory.

Example 8 .7 1; g. of alphamethylbenzylrbetacyanethoxyethyl ether was .intimately mixed .with- 10; g.1;:of a copolymer-containing- %:w-.-/W ofi'yinylpidene ...,.chloride and 10 of '1 vinyl chloride, by; stirring .with ace-tones and .then-.-- -eyaporating:;' ,solvent. ..'-I.he v-.c,o mposition- ,was; presse -chromiumeplated mould rat :9,- t0.;.;give.' 1 ...about /8 :thick. ;The composition z-sho,wedgood ....fiow,.;andl-gave:no evidence ofadecoinposition, the disc obtained being pale yellow and translucent. 70 A similar compositionjwas prepared from 1 g. of the above ether and'ilO g. of a copolymer containing 95% w./w. "-vinylidene chloride and :5 %-.acry1onitri1e, ,tTl'llS." composition was'z'pressed -..,in az'mould eat CuutQJgiVGI. azzpalea-amber- 75.,coloured disc ,..sh0win good .floW.

, Example 9 An intimate mixture was prepared from 1 g. of alphamethylbenzyl 4-cyanbutyl ether and g. of a copolymer containing 90% w./w. of vinylidene chloride and 10% of vinyl chloride. A disc thick was moulded fromthis composition at "a temperature of 170 and pressure'of'SOOO lb. p. s. i. A pale amber-coloured moulding resulted which showed good flow.

The above procedure was repeated with a copolymer containing 86% w./w. of vinylidene chloride, 12% of vinyl chloride and 2% of acrylonitrile. The resulting disc showed very gOOd flow and was of a pale amber colour.

Example 10 1 g. of alphamethylparachlorbenzyl betacyanethyl ether and 10 g. of a copolymer containing 90% w./w. of vinylidene chloride and 10% of vinyl chloride were mixed intimately by adding acetone and stirring, and the acetone was removed by evaporation. A portion of the composition was extruded through a nozzle s 5 in diameter at a temperature of 170 to give a clear, almost colourless monofilament showing no signs of decomposition.

A further portion of the composition was pressed in a chromium-plated mould at a temperature of 1'75-180. The material flowed freely to give a tough, translucent, pale yellow disc t thick.

Example 11 A series of compositions of polyvinylidene chloride and plasticiser were prepared by treating the powdered polymer with a solution of plasticiser in acetone, stirring thoroughl and evaporating off the acetone. The resulting compositions were pressed at 180 C. in a nickel mould to give discs 1 in diameter and thick. The plasticisers used and the appearance of the discs obtained are detailed in the following table:

tgl'oncentra- Plasticlser fiff gfg figg Appearance of disc resin Per cent Alphamethyl parachlorben- 10 Translucent, yellow,

zyl betacyanethyl ether. good flow.

Do 15 Translucent, yellow,

very ready flow. Alphamethyl 2:4-dimethyl- Very pale yellow, transe n z yl betacyanethyl lucent, good flow. ether.

Example 13 A number of discs were prepared by the method described in Example 12, using a copolymer containing 85% by weight of vinylidene chloride and 15% of vinyl chloride. Their composition and appearance are detailed in the following table:

Pale brown, fairly good zyl betacyauethyl ether. flow.

Pale orange, translu- Alphamethyl benzyl beta- 8 cyanethyl ether. cent, very good'flow. Alphamethyl benzyl beta- 10 Somewhat pllable, very cyanisopropyl ether. pale yellow. Alphamethyl 2:4-dimethy1- 5 Pale brovwi, fairly good benzyl betacyanethyl flow. ether.

The superiority of these novel plasticizers in respect of oxidation resistance as compared with those derived from benzyl alcohol can be seen from the following experiment.

Benzyl alcohol was reacted with acrylonitrile as described for phenylmethyl carbinol in Example 1, to give benzyl betacyanethyl ether, b. pt. IOU-102 C. under 2 mm. mercury pressure, 12 1.5128. A small quantity of this ether was placed in a watch glass, covered loosely with a second watch glass and allowed to stand in diffuse light at room temperature. After two weeks, the sample had acquired a strong odour of benzaldehyde, but no such oxidative change has been observed in similarly exposed samples of alphamethylbenzyl betacyanethyl ether or of any of the other cyanalkyl ethers described herein.

While the resins mentioned in the foregoing examples are mainly vinylidene chloride polymers and copolymers with vinyl chloride, it will be appreciated that the novel stabilisers may also be employed with other vinylidene chloride coolymers, which may incorporate two, three or more different monomeric units. Suitable examples of the latter include vinyl esters of organic acids such as vinyl acetate, vinyl methoxybutyrate and vinyl laurate, esters of acrylic, alphachloracrylic and alphamethacrylic acids with alkyl and cycloalkyl radicals of six or less carbon atoms, such as cyclohexyl methacrylate, butyl acrylate and ethyl chloracrylate, diesters of itaconic, maleic and fumaric acids with alkyl and cycloalkyl radicals of six or less carbon atoms, acrylonitrile, methacrylonitrile and crotononitrile.

Substances described but not claimed herein are claimed in my copending application, Serial No. 188,486, filed October 4, 1950.

I claim:

1. A plasticised composition comprising a polymeric resin containing a major proportion of vinylidene chloride units in its molecular structure and 5-20%, based on the weight of the resin, of a compound of the formula where X1 is a radical selected from the group consisting of the phenyl, monoand dichlorophenyl and monoand dimethyl phenyl radicals, R1 is an alkylene radical of 2-4 carbon atoms, to each of which carbon atoms is attached at least 1 hydrogen atom, and n is an integer from 0 to 1.

2. A plasticised composition as set forth in claim 1, wherein R1 is an ethylene radical.

3. A plasticised composition as set forth in claim 1, wherein R1 is a propylene radical and the nitrile group is connected directly to a methylene group thereof.

4. A plasticised composition as set forth in claim 1, wherein R1 is a tetramethylene radical.

7 5.-A---plasi1ioised composition as set forthin claim 1, wherein thepolymeric resin is a vinylidenedchlorideevinyl" chloride copolymer:

6. A plasticised "composition as set forth in claim 1, wherein the polymericuresin is V poly-1 vinylidene chloride.

75A plasticised composition as set'forth "in claim 1, wherein the resin is a copolymer of inylidene chloride, vinyl chloride, and'acrylonitrile.

8. Av plasticised composition as set forth .in

claim'l wherein said compound is alphametlryl benzyl beta cyan ethyl ether;

9. ,A ,plasticised composition as set forth in claim ,1 wherein said compound is alpha methyl zzi dimethyl .benzyl beta cyan ethyl ether,

IOLA' plasticised composition asset forthiin claim 1 wherein said eompoundis alpharmethyl benzyl beta-cyan ethoxy-ethyl ether,

11. A plasticisemcomposifion as set forth in claim .1 wherein said compound isalpha methyl benzyl 4 cyan butyl ether. DONALD'FAULKNERI REFERENCES CITED The followingreferences are of .record inthe file of thispatent:

UNITED STATES PATENTS Number 7 Name Date 2,239,515 Bartlett et al Apr. 22;19'41 2,319,634 Sauser May \18, 1943 2,337,635 Bogin Deor28y1943' 2,372,615 'Ihomaset al: M21227, 1945 2,435,869 Bruson et al. Feb. 10, 1948 2,437,905 Bruson et al. Mar. 16, 1948 

1. A PLASTICISED COMPOSITION COMPRISING A POLYMERIC RESIN CONTAINING A MAJOR PROPORTION OF VINYLIDENE CHLORIDE UNITS IN ITS MOLECULAR STRUCTURE AND 5-20%, BASED ON THE WEIGHT OF THE RESIN, OF A COMPOUND OF THE FORMULA 